Method of processing silver halide color photographic materials

ABSTRACT

A method for processing a silver halide color photographic material comprising at least one silver halide emulsion layer, which comprises developing the silver halide color photographic material with a color developer containing at least one aromatic primary amine color developing agent, wherein the photographic material contains (a) at least one high silver chloride content emulsion layer with a silver chloride content of 80 mol % or more, and (b) a compound of formula (I): ##STR1## wherein R 1  and R 2  each represents --COOR 5 , ##STR2## --COR 5  --CN or a halogenated methane  R 3  and R 4  each represents a hydrogen atom or an unsubstituted or substituted alkyl group; R 5  and R 6  each represents a hydrogen atom, an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group; Q 1  and Q 2  each represents an aryl group; X 1  and X 2  each represents a chemical bond or a divalent linking group; Y 1  and Y 2  each represents a sulfo group or a carboxy group; L 1 , L 2  and L 3  each represents a methine group; m 1  and m 2  each represents 0, 1, or 2; n represents 0, 1 or 2; p 1  and p 2  each represents 0, 1, 2, 3 or 4; s 1  and s 2  each represents 1 or 2; and t 1  and t 2  each represents 0 or 1; provided that the total of m 1 , p 1  and t 1  and the total of m 2 , p 2  and t 2  must not be 0 at the same time; 
     and the color developer contains a chloride ion in an amount of from 3.5×10 -2  to 1.5×10 -1  mol/liter and bromide ion in an amount of from 3.0×10 -5  to 1.0×10 -3  mol/liter.

This is a Continuation of application Ser. No. 07/416,636 filed Oct. 3,1989, abandoned.

FIELD OF THE INVENTION

The present invention relates to a method for processing a silver halidecolor photographic material and, more precisely, to a method forprocessing a high silver chloride silver halide photographic materialwhich has excellent developability and desilvering property. It furtherrelates to a method for processing such a photographic material to givea processed material with an improved white background portion with lessstain even by rapid processing.

BACKGROUND OF THE INVENTION

Recently, in photographic processing of color photographic materials,shortening of the processing time is desired to bring about a shorteningof the period for delivery of finished photographs and a reduction inlabour in the photo-processing laboratory. As a means of shortening theprocessing time in the respective processing steps, elevating theprocessing temperature and increasing the replenisher to each step havebeen generally used. In addition, other various methods of strengtheningstirring or adding various accelerators have heretofore been proposed.

Above all, a method of processing a color photographic materialcontaining a silver chloride emulsion in place of a silver bromide typeemulsion or silver iodide type emulsion which has hitherto widely beenused is noticeable for the purpose of accelerating color developmentand/or reducing the amount of the replenisher. For instance,International Patent Application Laid-Open No. W087-04534 illustrates amethod of rapid processing of a high silver chloride color photographicmaterial with a color developer substantially not containing sulfite ionand benzyl alcohol.

However, the above rapid processing method was found to have someserious problems, especially in the continuous processing procedure, inthat the non-colored portion (hereinafter referred to as "whitebackground portion") in the processed color photographic material isstained (colored in the white background portion) so that it becomesdirty, and further the image portion (colored portion) is insufficientlydesilvered so that the color reproducibility and the saturation are low.

As the main reasons for causing the abovementioned stains, there arementioned the following points:

(1) The non-exposed portion is silver-developed or fogged.

(2) The oxidized products (e.g., tar component, etc.) of the colordeveloping agent and the like adhere to the photographic material beingprocessed to cause color staining on the material.

(3) After the color development step, the developing agent is carriedover into the oxidation bath (bleaching bath or bleach-fixation bath)where the agent is oxidized to thereby be discriminatingly coupled withthe coupler existing in the photographic material being processed toform a dye therein. This is a so-called bleaching fog.

(4) Because of insufficient washing of the antiirradiation dye andsensitizing dye from the processed photographic material, the colors ofthe dyes still remain in the processed material. This is a so calledcolor-retention.

Accordingly, prevention of stain in the white background portion couldbe attained only after the stains caused by the above-mentioned points(1) through (4) be totally improved and prevented.

On the other hand, the desilvering failure caused by high silverchloride emulsions would result from the following reasons:

That is, a silver chloride emulsion has a higher silver ion-solubilitythan a silver iodobromide or silver chlorobromide emulsion and, as aresult, the development of a silver chloride emulsion may finish in ashort period of time because of extreme acceleration of the solutionphysical development of the emulsion. However, the developed silver thusformed is hardly in the form of filaments, but nearly spherical andlarge developed silver grains having a small surface area would beformed and, as a result, the desilvering speed would be lowered.

As a means of overcoming the above-mentioned problems, methods of usingan organic antifoggant are known, for example, as described inJP-A-58-95345 and JP-A-59-232342 (the term "JP-A" as used herein meansan "unexamined published Japanese patent application"), where a highsilver chloride color photographic material is processed by continuousrapid processing whereupon fluctuation of the photographiccharacteristic (especially anti-fogging property) of the photographicmaterial being processed is reduced by the action of the organicantifoggant. However, it has been found that incorporation of such anorganic antifoggant into the photographic material would often cause alowering of the maximum density of the image formed in the material andwould often cause desilvering failure (unsufficient desilvering) in theprocessing step. Accordingly, the method of using such an organicantifoggant could not be said favorable.

On the other hand, JP-A-61-70552 illustrates a method of processing ahigh silver chloride color photographic material by a low-replenishmentsystem where a replenisher is added to the development bath in such anamount that the developer does not overflow from the development bathduring the processing. JP-A-63-106655 illustrates a method of processinga silver halide color photographic material in which the silver halideemulsion layer has a high silver chloride content, with a colordeveloper containing a hydroxyamine type compound and at least 2×10⁻²mol/l of a chloride, with an object of providing a stabilizedprocessing.

However, both of the above methods were not effective for preventing thegeneration of stains and were unsatisfactory for improving thedesilverability of the processed materials, and thus were notsatisfactory techniques.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a method ofprocessing a high silver chloride color photographic material by rapidprocessing to give a color image with no stain on the materialprocessed.

A second object of the present invention is to provide a method ofprocessing a high silver chloride color photographic material by rapidprocessing to give a color image having an excellent photographicproperty with a high maximum density and a low minimum density,whereupon fluctuation of the photographic characteristic (especially,the minimum density) is noticeably retarded even in continuousprocessing.

A third object of the present invention is to provide a method ofprocessing a high silver chloride color photographic material, in whichthe residual silver amount in the processed material is small and thedesilverability of the material has been improved.

It has been found in accordance with the present invention that theabove-mentioned and other objects can effectively be attained by amethod for processing a silver halide color photographic materialcomprising at least one silver halide emulsion layer, which comprisesdeveloping the photographic material with a color developer containingat least one aromatic primary amine color developing agent, wherein thephotographic material contains (a) at least one high silver chloridecontent emulsion layer with a silver chloride content of 80 mol% ormore, and (b) a compound of formula (I): ##STR3## wherein R₁ and R₂ eachrepresents --COOR₅, ##STR4## --COR₅ --CN or a halogenated methane; R₃and R₄ each represents a hydrogen atom or an unsubstituted orsubstituted alkyl group; R₅ and R₆ each represents a hydrogen atom, anunsubstituted or substituted alkyl group having 1 to 10, preferably 1 to5 carbon atoms or an unsubstituted or substituted aryl group having 6 to10 carbon atoms; Q₁ and Q₂ each represents an unsubstituted orsubstituted aryl group having 6 to 10 carbon atoms; X₁ and X₂ eachrepresents a chemical bond or a divalent linking group; Y₁ and Y₂ eachrepresents a sulfo group or a carboxy group; L₁, L₂ and L₃ eachrepresents a methine group; m₁ and m₂ each represents 0, 1, or 2; nrepresents 0, 1 or 2; p₁ and p₂ each represents 0, 1, 2, 3 or 4; s₁ ands₂ each represents 1 or 2; and t₁ and t₂ each represents 0 or 1;provided that the total of m₁, p₁ and t₁ and the total of m₂, p₂ and t₂must not be 0 at the same time;

and the color developer contains chloride ion in an amount of from3.5×10⁻² to 1.5×10⁻¹ mol/liter and bromide ion in an amount of from3.0×10⁻⁵ to 1.0×10⁻³ mol/liter.

DETAILED DESCRIPTION OF THE INVENTION

Chloride ion is well known as one of the conventional antifoggants, butthe effect thereof is poor. Even though a large amount of chloride ionis used, an increase of fog with continuous processing and streaky fogswhich are generated in processing with an automatic developing machinecould not completely be prevented, but rather the use of such a largeamount of chloride ion would have a bad influences on the processing ofphotographic materials, for example, the development would be retardedor the maximum density would be lowered.

Bromide ion is also well known as one of the conventional antifoggants.Where the amount of the bromide ion to be used is properly controlled,fogging in continuous processing during development could be prevented.However, the bromide ion also inhibits the development in the continuousprocessing of photographic materials thereby to lower the maximumdensity and the sensitivity of the materials. Accordingly, bromide ioncould not be put to practical use.

On the other hand, various dyes are incorporated into silver halidecolor photographic materials for the purpose of preventing irradiationin printing or for the purpose of elevating the safety to a so-calledsafe light, the dyes not lowering the sensitivity of the materials, notworsening the latent image-preservability thereof and not having anyother bad influences on the photographic characteristics of thematerials and additionally the dyes not causing stains (such ascolor-retention stains) in the processed materials to lower the qualitythereof.

These dyes often color the processed color photographic materials tocause undesirable stains therein, where the materials are insufficientlywashed after being processed or where the dyes are dissolved out intothe color developer, the rinsing water and/or the stabilizing solutionto inconveniently color the processing solutions, and such would be aserious problem especially in rapid processing. In order to prevent suchstains (color stains) from being caused by the dyes, it is generallydesired to employ dyes that can be decomposed with alkalis or reducingagents in the color developer to give colorless products. Additionally,in rapid processing, washing of the dyes and decoloration thereof in thecolor developer are to be important techniques.

In accordance with the present invention, a determined amount ofchloride ion and a determined amount of bromide ion are incorporatedinto the color developer to be employed in the method of the presentinvention, whereby fog during development has successfully beeninhibited without lowering the maximum density. Additionally, the effectof washing the dyes of the above-mentioned formula (I) in the colordeveloper may be accelerated even in rapid processing, and releasing ofthe sensitizing dyes from the photographic material being processed maybe accelerated. As a result, stain may be prevented and, for example, aphotograph with an excellent white background portion can be obtained inaccordance with the present invention.

In particular, it is especially noted that the desilverability in themethod of the present invention has extremely been improved because ofthe incorporation of bromide ion of a determined concentration andchloride ion of a determined concentration into the color developer tobe employed and of the incorporation of the dye of the above-mentionedformula (I) into the photographic material to be processed by the methodof the present invention. Above all, it is particularly noted that theabove effect can be attained by the employment of the dye having thestructure of formula (I).

Now, the present invention will be explained in detail hereunder.

The silver halide emulsion which constitutes the photographic materialto be processed by the method of the present invention substantiallycomprises silver chloride. The wording "substantially comprises silverchloride" as referred to herein means that the content of silverchloride to the total silver halide is 80 mol% or more, preferably 95mol% or more, more preferably 98 mol% or more. In view of the rapidprocessability of the material, the silver chloride content ispreferably as high as possible.

The amount of silver which is coated on the silver halide photographicmaterial of the present invention is preferably 0.80 g/m² or less, inview of the rapid processability high desilverability and sufficientstainpreventability. Such merits are considered to be caused by not onlythe reduction of the silver amount in the material but also thereduction of the film thickness of the material. The amount of silvercoated on the material is more preferably 0.75 g/m² or less, especiallypreferably 0.65 g/m² or less. In view of the image density, however, itis preferably 0.30 g/m² or more.

In accordance with the present invention, it is necessary that the colordeveloper contains chloride ion in an amount Of from 3.5×10⁻² to1.5×10⁻¹ mol/liter, preferably from 4×10⁻² to 1×10⁻¹ mol/liter. If thechloride ion concentration in the color developer is more than 1.5×10⁻¹mol/liter, the developer would have the drawback that the developabilityis retarded, and the object of the present invention to attain rapidprocessing and to obtain a high maximum density in the processedmaterial could not be attained. On the other hand, if it is less than3.5×10⁻² mol/liter, stain could not be prevented and, in addition,fluctuation of the photographic property (especially, the minimumdensity) would be large with continuous processing and the amount of theresidual silver would be large. Accordingly, the object of the presentinvention also could not be attained.

In accordance with the present invention, it is further necessary thatthe color developer contains bromide ion in an amount of from 3.0×10⁻⁵mol/liter to 1.0×10⁻³ mol/liter, preferably from 5.0×10⁻⁵ mol/liter to5×10⁻⁴ mol/liter. If the bromide ion concentration is more than 1×10³mol/liter, the development would be retarded and the maximum density andsensitivity would lower. However, if it is less than 3.0×10⁻⁵ mol/liter,prevention of stain could not be effected and, in addition, fluctuationof the photographic property (especially the minimum density) anddesilvering failure with continuous processing could not be prevented.Accordingly, the objects of the present invention also could not beattained.

The chloride ion and bromide ion may be added directly to the developeror, alternatively, they may be dissolved out from the photographicmaterial during processing.

Where the ions are directly added to the color developer, there arementioned sodium chloride, potassium chloride, ammonium chloride, nickelchloride, magnesium chloride, manganese chloride, calcium chloride andcadmium chloride as chloride ion-donating substances. Among them, sodiumchloride and potassium chloride are preferred.

The ions may also be introduced into the developer in the form ofcounter ions of the brightening agents which are added to the developer.As substances for donating bromide ion, there are mentioned sodiumbromide, potassium bromide, ammonium bromide, lithium bromide, calciumbromide, magnesium bromide, manganese bromide, nickel bromide, cadmiumbromide, cerium bromide and thallium bromide. Among them, potassiumbromide and sodium bromide are preferred.

Where the ions are to be dissolved out from the photographic materialsduring development, both may be derived from the emulsions or from othersources.

Next, formula (I) which represents the compounds which are incorporatedin the photographic materials of the present invention will be explainedin detail hereunder.

In formula (I), R₁ and R₂ independently represent --COOR₅, ##STR5##--COR₅ or --CN.

R₃ and R₄ each represents a hydrogen atom, an unsubstituted alkyl groupor a substituted alkyl group (e.g., methyl, ethyl, butyl, hydroxyethyl).R₅ and R₆ each represents a hydrogen atom, an unsubstituted alkyl orsubstituted alkyl group (e.g., methyl, ethyl, butyl, hydroxyethyl,phenethyl), or an unsubstituted aryl or substituted aryl group (e.g.,phenyl, hydroxyphenyl).

Q₁ and Q₂ each represents an unsubstituted or substituted aryl group(e.g., phenyl, naphthyl). X₁ and X₂ each represents a chemical bond or adivalent linking group (e.g., --S--, --O--, --Se--, --NH--, --CH₂ --);and Y₁ and Y₂ each represents a sulfo group or a carboxyl group. L₁, L₂and L₃ each represents a methine group. m₁ and m₂ each represents 0, 1or 2; n represents O, 1 or 2; p₁ and p₂ each represents 0, 1, 2, 3 or 4;s₁ and s₂ each represents 1 or 2; and t₁ and t₂ each represents 0 or 1;provided that the total of m₁, p₁ and t₁, and the total of m₂, p₂ and t₂must not be 0 at the same time.

Specific examples of the compounds of formula (I) are set forth below bycompounds (I-1) to (I-37), which, however, are not limitative. ##STR6##

The amount of the compound of formula (I) to be incorporated into thecolor photographic material is preferably from 0.0001 g to 1 g, morepreferably form 0.0005 g to 0.1 g, per m² of the material.

The dyes of formula (I) are generally used as an anti-irradiation dye,and thus compounds (I-1) to (I 37) are anti-irradiation dyes. Ingeneral, the dyes of formula (I) are incorporated into the silver halideemulsion layer and especially preferably into the green-sensitiveemulsion layer or red-sensitive emulsion layer.

In accordance with the present invention, it is preferred that the colordeveloper does not substantially contain sulfite ion in view ofmaintaining the processing stability in continuous processing and ofpreventing streaky pressure marks. For the purpose of preventingdeterioration of the color developer during processing, various physicalmeans are employed, for example, the developer is not used for a periodof too long a time, a floating lid is used so as to prevent theinfluence of aerial oxidation and the opening area of the developer tankis reduced, or various chemical means are also employed, for example,the temperature of the developer is lowered and an organic preservativeis added to the processing solution. Above all, employment of organicpreservatives is advantageous as being simple.

The organic preservative as referred to herein means any and everyorganic compound which can be added to the processing solution for colorphotographic materials thereby to retard the deteriorating speed of thearomatic primary amine color developing agent contained in thedeveloper. That is to say, such organic preservatives include organiccompounds having a function of preventing aerial oxidation of colordeveloping agents. Above all, effective organic preservatives arehydroxylamine derivatives excluding unsubstituted hydroxylamine (hereinafter referred to as "hydroxylamine derivatives"), hydroxamic acids,hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones,saccharides, monoamines, diamines, polyamines, quaternary ammoniumsalts, nitroxy radicals, alcohols, oximes, diamide compounds andcondensed ring type amines. These are described in JP-A-63-146041, JP-A63-170642, JP-A-63-4235, JP-A-63-30845, JP-A 63-21647, JP-A-63-44655,JP-A-63-53551, JP-A-63-43140, JP-A-63-56654, JP-A-63-58346,JP-A-63-43138, JP-A-63-44657, JP-A-63-44656, and JP-A-52-143020, U.S.Pat. Nos. 3,615,503 and 2,494,903 and JP-B-48-30496. (The term "JP-B" asreferred to herein means an "examined Japanese patent publication".)

For the preferred organic preservative, the constitutional formulaethereof as well as specific examples of the compounds thereof will bementioned below, which, however, are not intended to restrict the scopeof the present invention.

The amount of the organic preservative compound to be added to the colordeveloper is desirably from 0.005 mol/liter to 0.5 mol/liter, preferablyfrom 0.03 mol/liter to 0.1 mol/liter.

In particular, addition of hydroxylamine derivatives and/or hydrazinederivatives is preferred.

As hydroxylamine derivatives, those of the following formula (II) arepreferred. ##STR7## wherein R²¹ and R²² each represents a hydrogen atom,an unsubstituted or substituted alkyl group, an unsubstituted orsubstituted alkenyl group, an unsubstituted or substituted aryl group oran unsubstituted or substituted hetero-aromatic group. R²¹ and R²² mustnot be hydrogens at the same time, and they may be bonded to each otherto form a hetero-ring together with the adjacent nitrogen atom. Thecyclic structure of the hetero ring is 5-membered or 6-membered, and itis composed of carbon, hydrogen, halogen, oxygen, nitrogen and/or sulfuratoms. It may be either saturated or unsaturated.

Preferably, R²¹ and R²² each represents an alkyl group or an alkenylgroup, and the group preferably has from 1 to 10 carbon atoms,especially preferably from 1 to 5 carbon atoms. As thenitrogen-containing hetero-ring to be formed of R²¹ and R²² as bonded toeach other, there are mentioned a piperidyl group, a pyrrolidyl group,an N-alkylpiperazyl group, a morpholyl group, an indolinyl group and abenzotriazole group.

Preferred substituents on R²¹ and R²² are a hydroxyl group, an alkoxygroup, an alkyl sulfonyl group, an arylsulfonyl group, an amido group, acarboxyl group, a cyano group, a sulfo group, a nitro group and an aminogroup.

Examples of the compounds of the formula (II) are as follows: ##STR8##

As hydrazines and hydrazides, those of the following formula (III) arepreferred. ##STR9## wherein R³¹, R³² and R³³ each represents a hydrogenatom, or a substituted or unsubstituted alkyl, aryl or heterocyclicgroup; and R34 represents a hydroxyl group, a hydroxylamino group, or asubstituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy,carbamoyl or amino group. The heterocyclic group is a 5-membered or6-membered group and is composed of C, H, O, N, S and/or halogen atoms.It may be either saturated or unsaturated. X³¹ represents a divalentgroup selected from --CO--, --SO₂ -- or ##STR10## and n represents 0or 1. In particular, when n is 0, R³⁴ represents a group selected froman alkyl group, an aryl group and a heterocyclic group, or R³³ and R³⁴may together form a hetero-ring.

In formula (III), R³¹, R³² and R³³ preferably represent hydrogen atomsor alkyl groups having 1 to 10 carbon atoms, and more preferably R³¹ andR³² are hydrogen atoms.

In formula (III), R³⁴ preferably represents an alkyl group, an arylgroup, an alkoxy group, a carbamoyl group or an amino group, and morepreferably it is an unsubstituted alkyl group or a substituted alkylgroup. Preferred substituents for the alkyl group are a carboxyl group,a sulfo group, a nitro group, an amino group and a sulfono group. X³¹preferably represents --CO-- or --SO₂ --, and more preferably, it is--CO--.

Examples of compounds of formula (III) are as follows: ##STR11##

Employment of a compound of the above-mentioned formula (II) or (III)and an amine compound of the following formula (IV) or (V) incombination is more preferred for the purpose of improving the stabilityof the color developer and especially for improving the stability of thecolor developer in continuous processing. ##STR12## wherein R⁷¹, R⁷² andR⁷³ each represents a hydrogen atom, an alkyl group, an alkenyl group,an aryl group, an aralkyl group or a heterocyclic group. In formula(IV), R⁷¹ and R⁷² ; R⁷¹ and R⁷³ ; or R⁷² and R⁷³ may be bonded to eachother to form a nitrogen-containing hetero-ring.

R⁷¹, R⁷² and R⁷³ may have substituent(s). Especially preferably, R⁷¹,R⁷² and R⁷³ each is a hydrogen atom or an alkyl group. As thesubstituent(s}for these groups, there are mentioned a hydroxyl group, asulfo group, a carboxyl group, a halogen atom, a nitro group and anamino group.

Examples of compounds of formula (IV) are mentioned below. ##STR13##wherein X represents a trivalent atomic group necessary for completingthe condensed ring; and R¹ and R² each represents an alkylene group, anarylene group, an alkenylene group or an aralkylene group, and R¹ and R²may be the same or different.

Among the compounds of formula (V), especially preferred are those ofthe following formulae (V-a) and (V-b); ##STR14## wherein X¹ represents##STR15## R¹ and R² have the same meanings as those defined in formula(V); and R³ has the same meaning as R¹ and R² of formula (V), orrepresents ##STR16##

In formula (V-a), X¹ is preferably ##STR17## The number of the carbonatoms in the group R¹, R² or R³ is preferably 6 or less, more preferably3 or less, most preferably 2 or less.

Preferably, R¹, R² and R³ each is an alkylene group or an arylene group;and most preferably, each is an alkylene group. ##STR18## wherein R¹ andR² have the same meanings as those defined in formula (V).

In formula (V-b), the number of carbon atoms in R¹ or R² is preferably 6or less. Preferably, R¹ and R² each is an alkylene group or an arylenegroup, and more preferably each is an alkylene group.

Of the compounds of formulae (V-a) and (V-b), especially preferred arethe compounds of formula (V-a).

Examples of compounds of formula (V) are mentioned below. ##STR19##

The above-mentioned organic preservatives as represented by the formulae(II) to (V) are available as commercial products, and some of them canbe produced by the methods described in JP-A-63-170642 andJP-A-63-239447.

Next, the color developer for use in the present invention will bedescribed below.

The color developer which can be employed in the method of the presentinvention contains a known aromatic primary amine color developingagent. Preferred examples of the developing agent arep-phenylenediamines, and some typical examples thereof are mentionedbelow, which, however, are not limitative.

D-1: N,N-diethyl-p-phenylenediamine

D-2: 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D-3: 2-Methyl-4-[N-ethyl-N (β-hydroxyethyl)amino]aniline

D-4: 4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline

The p-phenylenediamines may be in the form of their salts, such assulfates, hydrochlorides or p-toluene-sulfonates. The amount of thearomatic primary amine developing agent in the developer is preferablyfrom about 0.1 g to about 20 g, more preferably from about 0.5 g toabout 10 g, per liter of the developer. ##STR20##

The color developer for use in the present invention has a pH value ofpreferably from 9 to 12, more preferably from 9 to 11.0. The colordeveloper may contain further compounds of known developer components.

In order to maintain the above-mentioned pH range, various buffers arepreferably added to the color developer. As examples of buffers usablefor this purpose, there are mentioned sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium bicarbonate, trisodiumphosphate, tripotassium phosphate, disodium phosphate, dipotassiumphosphate, sodium borate, potassium borate, sodium tetraborate (borax),potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium5-sulfosalicylate).

The amount of the buffer to be added to the color developer ispreferably 0.1 mol/liter or more, especially preferably from 0.1mol/liter to 0.4 mol/liter.

In addition, the color developer may further contain various chelatingagents, as an agent for preventing precipitation of calcium or magnesiumor for the purpose of improving the stability of the developer.

Examples of chelating agents usable for the purpose are mentioned below,which, however, are not limitative. They include nitrilotriacetic acid,diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid,triethylene-tetramine-hexaacetic acid, N,N,N-trimethylene-phosphonicacid, ethylenediamine-N,N,N',N'-tetramethylene-phosphonic acid,1,3-diamino-2-propanol-tetraacetic acid,transcyclohexanediaminetetraacetic acid, nitrilo-tripropionic acid,1,2-diaminopropane-tetraacetic acid, hydroxyethylimino-diacetic acid,glycoletherdiamine-tetraacetic acid, hydroxyethylenediamine-triaceticacid, ethylenediamine-orthohydroxyphenylacetic acid,2-phosphonobutane-1,2,4 tricarboxylic acid,1-hydroxyethylidene-1,1-diphosphonic acid,N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid,catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid,5-sulfosalicylic acid and 4-sulfosalicylic acid.

Two or more of such chelating agents may be used in combination, ifdesired.

The amount of the chelating agent to be added to the color developer maybe such that is sufficient for sequestering the metal ions in the colordeveloper. For instance, it may be from 0.1 g to 10 g or so per liter ofthe color developer.

The color developer may also contain a development accelerator, ifdesired.

As examples of development accelerators usable in the present invention,there are mentioned thioether compounds described in JP-B-37-16088,JP-B-37 5987, JP-B-38-7826, JP-B-44-12380 and JP-B-45-9019 and U.S. Pat.No. 3,813,247; p-phenylenediamine compounds described in JP-A-52-49829and JP-A-50-15554; quaternary ammonium salts described inJP-A-50-137726, JP-B-4430074 and JP-A-56-156826 and JP-A 52-43429;p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462;amine compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182,4,230,796, 3,253,919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926and 3,582,346; polyalkylene oxides described in JP-B-37-16088,JP-B-42-25201, U.S. Pat. No. 3,128,183, JP-B-41-11431 and JP B-42-23883and U.S. Pat. No. 3,532,501; and other 1-phenyl-3-pyrazolidones,hydrazines, mesoionic compounds and imidazoles. One or more of them maybe added to the color developer, if desired.

Preferably, the color developer for use in the present invention doesnot substantially contain benzyl alcohol. The wording "does notsubstantially contain benzyl alcohol" means that the color developercontains benzyl alcohol in an amount of 2.0 ml/liter or less and itpreferably contains no benzyl alcohol. Where the color developer doesnot substantially contain benzyl alcohol, fluctuation of thephotographic characteristic in continuous processing, especiallyincrease of stain, in small and a more favorable result can be obtained.

In accordance with the present invention, any other desired antifoggantcan be added to the color developer, in addition to chloride ion andbromide ion. As such antifoggant, for example, alkali metal halides suchas potassium iodide and organic antifoggants can be employed. Asexamples of organic antifoggants usable for the purpose, there arementioned nitrogen-containing heterocyclic compounds such asbenzotriazole, 6-nitrobenzimidazole, 5-nitroisoinadazole,5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,2-triazolyl-benzimidazole, 2-thiazolylmethylbenzimidazole, indazole,hydroxyazaindolidine and adenine.

The color developer for use in the present invention preferably containsa brightening agent. As the brightening agent are preferred4,4'-diamino-2,2'-disulfostilbene compounds. The amount thereof to beadded to the developer is up to 10 g/liter, preferably from 0.1 to 6g/liter.

In addition, the color developer may also contain various surfactants,if desired, such as alkylsulfonic acids, aryl-phosphonic acid, aliphaticcarboxylic acids or aromatic carboxylic acids.

The processing time with the color developer in accordance with thepresent invention is from 10 seconds to 120 seconds, preferably from 20seconds to 60 seconds, in order to remarkably attain the effect of thepresent invention. The processing temperature is from 33° to 45° C.,preferably from 36° to 40° C., whereupon the effect of preventing stainsis especially noticeable.

The amount of the replenisher to be replenished to the color developerbath in continuous processing is from 20 to 220 ml, especiallypreferably from 40 to 140 ml, per m² of the photographic material beingprocessed, whereupon the effect of the present invention is favorablyattained.

In accordance with the present invention, the photographic material isdesilvered, after it has been color-developed. The desilvering stepgenerally comprises a bleaching step and a fixation step. Especiallypreferably, bleaching and fixation are effected simultaneously.

The bleaching solution or bleach-fixing solution to be used in thepresent invention can contain a rehalogenating agent such as bromides(e.g., potassium bromide, sodium bromide, ammonium bromide), orchlorides (e.g., potassium chloride, sodium chloride, ammoniumchloride), or iodides (e.g., ammonium iodide). If desired, the solutionmay further contain a corrosion-inhibitor, such as one or more inorganicacids or organic acids having a pH buffering capacity or alkali metal orammonium salts thereof, for example, boric acid, borax, sodiummetaborate, acetic acid, sodium acetate, sodium carbonate, potassiumcarbonate, phosphorous acid, phosphoric acid, sodium phosphate, citricacid, sodium citrate or tartaric acid, as well as ammonium nitrate orguanidine.

The fixing agent to be used in the bleach-fixing solution or fixingsolution to be employed in the present invention may be a knownbleaching agent, i.e., a water-soluble silver halide solvent, forexample, thiosulfates such as sodium thiosulfate or ammoniumthiosulfate; thiocyanates such as sodium thiocyanate or ammoniumthiocyanate; or thioether compounds or thioureas such asethylenebis-thioglycolic acid or 3,6-dithiia-1,8-octanediol. Thesecompounds can be used singly or in combination of two or more of them.In addition, a particular bleach-fixing solution comprising acombination of a fixing agent and a large amount of a halide such aspotassium iodide, as described in JP-A-55-155354, can also be used. Inaccordance with the present invention, use of thiosulfates, especiallyammonium thiosulfate, is preferred. The amount of the fixing agent inthe solution is preferably from 0.3 to 2 mols, more preferably from 0.5to 1.0 mol, per liter of the solution.

The pH range of the bleach-fixing solution or fixing solution for use inthe present invention is preferably from 3 to 8, especially preferablyfrom 4 to 7. If the pH value of the solution is lower than the aboverange, deterioration of the solution and formation of leuco dyes fromthe cyan dyes are disadvantageously accelerated although the desilveringproperty of the solution would be higher. On the contrary, if the pHrange is higher than the above range, the desilvering speed would belowered and stains would be formed.

In order to adjust the pH value of the solution, hydrochloric acid,sulfuric acid, nitric acid, acetic acid, bicarbonates, ammonia,potassium hydroxide, sodium hydroxide, sodium carbonate or potassiumcarbonate can be added to the solution.

The bleach-fixing solution may further contain other various agents,such as a brightening agent, antifoaming agent or surfactant, as well asan organic solvent such as polyvinyl pyrrolidone or methanol, ifdesired.

The bleach-fixing solution or fixing solution for use in the presentinvention may contain a sulfite ionreleasing compound, for example,sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite),bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassiumbisulfite), or metabisulfites (e.g., potassium metabisulfite, sodiummeta-bisulfite, ammonium metabisulfite), as a preservative. Thecompounds are preferably incorporated into the solution in an amount offrom about 0.02 to about 0.50 mol/liter, more preferably from about 0.04to about 0.40 mol/liter, as the sulfite ion. In particular,incorporation of ammonium sulfite is preferred.

As the preservative for the bleach-fixing solution or fixing solution,sulfites are generally employed, but additionally, ascorbic acid,carbonyl-bisulfite adducts, sulfinic acids, carbonyl compounds orsulfinic acids may also be added to the solution.

In addition, a buffer, brightening agent, chelating agent and fungicidecan also be added to the solution, if desired.

In accordance with the present invention, the processing time with thebleach-fixing solution is from 10 seconds to 120 seconds, preferablyfrom 20 seconds to 60 seconds. The amount of the replenisher to thebleachfixing step is from 30 ml to 250 ml, preferably from 40 ml to 150ml, per m² of the photographic material being processed. Thus, in thepresent invention, the amount of the replenisher could be reduced ascompared to that amount generally used in the bleach fixing step (300 mlto 1000 ml per m² of the photographic material). In general, a decreaseof the replenisher would often be accompanied by an increase of stainsor a desilvering failure. However, the method of the present inventionis free from such problems and the amount of the replenisher to thebleach-fixing bath can be effected with no trouble.

In accordance with the present invention, the silver halide colorphotographic materials are generally rinsed in water and/or stabilized,after being desilvered by fixation or bleach-fixation.

The amount of water to be used in the rinsing step can be set in a broadrange, in accordance with the characteristic of the photographicmaterial being processed (for example, depending upon the raw materialcomponents, such as the coupler and so on) or the use of the material,as well as the temperature of the rinsing water, the number of therinsing tanks (the number of the rinsing stages}, the replenishmentsystem of co-current or countercurrent and other various kinds ofconditions. Among these conditions, the relation between the number ofthe rinsing tanks and the amount of the rinsing water in a multi-stagecountercurrent rinsing system can be obtained by the method described inJournal of the Society of Motion Picture and Television Engineers, Vol.64, pages 248 to 253 (May, 1955).

According to the multi-stage countercurrent system described in theabove-reference, the amount of the rinsing water to be used can bereduced noticeably, but because of the prolongation of the residencetime of the water in the rinsing tank, bacteria would propagate in thetank so that the floating substances generated by the propagation ofbacteria would adhere to the surface of the material as it wasprocessed. Accordingly, the above system would often have a problem. Inthe practice of processing the photographic materials of the presentinvention, the method of reducing calcium and magnesium ions, which isdescribed in JP-A-62-288838, can extremely effectively be used forovercoming this problem. In addition, the isothiazolone compounds andthiabendazoles described in JP-A-57-8542; chlorine-containingbactericides such as chlorinated sodium isocyanurates; andbenzotriazoles and other bactericides described in H. Horiguchi,Chemistry of Bactericidal and Fungicidal Agents, and Bactericidal andFungicidal Techniques to Microorganisms, edited by Association ofSanitary technique, Japan, and Encyclopedia of Bactericidal andFungicidal Agents, edited by Nippon Bactericide and FungicideAssociation, can also be used.

The pH value of the rinsing water to be used for processing thephotographic materials of the present invention is from 4 to 9,preferably from 5 to 8. The temperature of the rinsing water and therinsing time can also be set variously in accordance with thecharacteristics of the photographic material being processed as well asthe use thereof, and in general, the temperature is from 15° to 45° C.and the time is from 20 seconds to 2 minutes, and preferably thetemperature is from 25° to 40° C. and the time is from 30 seconds to 1minute and 30 seconds.

Even when employing such a short-time rinsing, an increase of stains maybe prevented and good photographic characteristics can be obtained inaccordance with the method of the present invention.

Alternatively, the photographic materials of the present invention mayalso be processed directly with a stabilizing solution in place of beingrinsed with water. For the stabilization, any known method, for exampleas described in JP-A-57-8543, JP-A-58-14834, JP-A-59-184343,JP-A-60-220345, JP A 60-238832, JP-A-60-239784, JP-A-60-239749,JP-A-61-4054 and JP-A-61-118749, can be employed. In particular, astabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid,5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound or anammonium compound is preferably used.

In addition, the material can also be stabilized, following the rinsingstep. As one example thereof, there may be mentioned a stabilizing bathcontaining formalin and a surfactant, which is used as a final bath forpicture-taking color photographic materials.

The processing time as referred to herein is defined to be the time fromthe photographic material to be processed being first brought intocontact with the color developer to the time when the same material isfinally taken out form the final bath (generally, rinsing or stabilizingbath). In a rapid processing procedure where the processing time is 3minutes and 30 seconds or less, preferably 3 minutes or less, the effectof the present invention is especially remarkable.

Next, the silver halide color photographic materials to be processed bythe method of the present invention will be explained in detailhereunder.

The silver halide emulsion of the present invention substantiallycomprises silver chloride. The wording "substantially comprises silverchloride" as referred to herein means that the silver chloride contentin the total silver halide is 80 mol% or more, preferably 95 mol% ormore, more preferably 98 mol% or more. The silver chloride content inthe silver halide emulsion is preferably as hi9h as possible, from theview point of the rapid processability of the emulsion. The high silverchloride emulsion may contain a small amount of silver bromide or silveriodide. Incorporation of such silver halide would often be favorable forthe purpose of increasing the light absorption in view of thelight-sensitivity of the emulsion, strengthening the adsorbability ofspectral sensitizing dyes in the emulsion or weakening thedesensitization by spectral sensitizing dyes therein.

The silver halide grains contained in the photographic emulsion layer ofthe photographic material to be processed by the method of the presentinvention may have different phases in the inside and the outer surfaceof the grain, or may have a multi-layer structure with a junctionstructure, or may have a uniform phase throughout the whole grain. Theemulsion may comprise various grains of different structures in mixture.

The silver halide grains in the photographic emulsion may be thosehaving a regular crystalline form such as a cubic, octahedral ortetradecahedral crystalline form, or those having an irregularcrystalline form such as a spherical or tabular crystalline form, orthose having a crystal defect such as a twin plane, or may also be thosehaving a composite form of such various crystal forms.

Regarding the grain size of the silver halide grains in the emulsion,the grains may be fine grains having a grain size of about 0.2 micron orless or may be large grains having a grain size (diameter of projectedarea) of up to about 10 microns. The emulsion may either be apolydispersed emulsion or a monodispersed emulsion.

The monodispersed emulsion used in the present invention is an emulsionhaving a grain size distribution such that a coefficient of variationwith respect to grain diameter of silver halide grains, S/r, is not morethan about 0.15, wherein S represents a standard deviation with respectto grain size, and r represents an average grain diameter.

The average grain diameter (r) and the standard deviation (S) aredefined by the following formulae, respectively: ##EQU1## wherein r_(i)represents a grain diameter of each emulsion grain, and n_(i) representsa number of the grains having the grain diameter of r_(i).

The term "grain diameter of each emulsion grain" as used herein means aprojected area-corresponding diameter which correponds to a diametercorresponding to an area projected at microphotographing the silverhalide emulsion by using a method which is well known in this art(normally using an electron microscope), as described in T. H. James etal., The Theory of the photographic Process, 3rd Ed., pp. 36-43,Macmillan Publishing Co., (1966). The projected area-correspondingdiameter of the silver halide grain is defined as a diameter of a circleequal to the projected area of the silver halide grain as shown in theabove-described literature by T. H. James et al. Therefore, even if theshape of the silver hlaide grain is not spherical form (e.g., cubic,octahedral, tetradecahedral, tabular, potato-like), the average graindiameter (r) and the standard deviation (S) can be measured.

The silver halide photographic emulsion for use in the present inventioncan be prepared, for example, in accordance with the method described inResearch Disclosure (RD), Item 17643 (December, 1978), pages 22 to 23,"I. Emulsion Preparation and Types".

Monodispersed emulsions described in U.S. Pat. Nos. 3,574,638 and3,655,394 and British Patent 1,413,748 are also preferably used in thepresent invention.

In addition, tabular grains having an aspect ratio of about 5 or moremay also be employed in the present invention. Such tubular grains caneasily be prepared in accordance with the methods described in Gutoff,Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970),U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and BritishPatent 2,112,157.

The crystal structure of the silver halide grains in the emulsion of thepresent invention may be uniform, or may comprise different halogencompositions in the inside and the outside, or may have a layeredstructure. Further, silver halides of different compositions may becombined by epitaxial junction to form one silver halide grain, or acompound other than silver halide, such as silver rhodanide or leadoxide, may be combined with silver halide to form on the silver halidegrain.

In addition, a mixture of grains of different crystalline structures mayalso be used in the present invention.

The silver halide emulsion for use in the present invention is generallyphysically-ripened, chemically-ripened or spectrally-sensitized.Additives which are used in these steps are described in ResearchDisclosure, Items 17643 and 18716, and the relevant parts are shown inthe Table below.

Other known photographic additives which are usable in the presentinvention are also mentioned in the above two literatures, and therelevant parts are also shown in the following Table.

    __________________________________________________________________________    Kinds of Additives                                                                           RD 17643  RD 18716                                             __________________________________________________________________________    1. Chemical Sensitizer                                                                       p. 23     p. 648, right column                                 2. Sensitivity-enhancer  "                                                    3. Spectral Sensitizer                                                                       pp. 23-24 from p, 648, right column to                            Super Color Sensitizer                                                                              p. 649, right column                                 4. Brightening Agent                                                                         p. 24                                                          5. Anti-foggant                                                                              pp. 24-25 p. 649, right column                                    Stabilizer                                                                 6. Light Absorbent                                                                           pp. 25-26 from p. 649, right column to                            Filter Dye            p. 650, left column                                     UV Absorbent                                                               7. Stain Inhibitor                                                                           p. 25, right column                                                                     p. 650, from left to right column                    8. Color Image Stabilizer                                                                    p. 25                                                          9. Hardening Agent                                                                           p. 26     p. 651, left column                                  10.                                                                              Binder      p. 26     "                                                       Plasticizer p. 27     p. 650, right column                                    Lubricant                                                                     Coating Aid pp. 26-27 "                                                       Surfactant                                                                    Antistatic Agent                                                                          p. 27     "                                                    __________________________________________________________________________

As sensitizing dyes which can be used in the present invention, those ofthe following formulae (VIa) and (VIb) are preferred, as they areeffective for preventing generation of stains and for improving thestability of the photographic characteristics in continuous processingof the high silver chloride color photographic material with the colordeveloper containing a determined amount of chloride ion and adetermined amount of bromide ion in accordance with the method of thepresent invention. ##STR21## wherein L represents an unsubstitutedmethine group or a substituted methine group;

R¹¹ and R¹² each represents an unsubstituted alkyl group or asubstituted alkyl group;

Z₁ and Z₂ each represents an atomic group necessary for forming anitrogen-containing 5-membered or 6-membered heterocyclic nucleus;

X⁻ represents an anion;

n represents a numerical value of 1, 3 or 5;

n₁ and n₂ each represents 0 or 1; when n is 5, both n₁ and n₂ are 0 andwhen n is 3, either n₁ or n₂ is 0; m represents 0 or 1, but m is 0 whenthe compound forms an inner salt;

when n is 5, the plural L groups may be bonded to each other to form asubstituted or unsubstituted 5-membered or 6-membered ring.

The cyanine dyes as represented by general formula (VIa) will beexplained in detail hereunder.

As the substituents for the substituted methine group of L, there arementioned a lower alkyl group (e.g., methyl, ethyl) and an aralkyl group(e.g., benzyl, phenethyl).

The alkyl group for R¹¹ and R¹² may be linear or branched or cyclic.Although not limitative, the number of the carbon atoms of the alkylgroup is preferably from 1 to 8, especially preferably from 1 to 4. Asthe substituents for the substituted alkyl group, there are mentioned,for example, a sulfonic acid group, a carboxylic acid group, a hydroxylgroup, an alkoxy group, an acyloxy group and an aryl group (e.g.,phenyl, substituted phenyl). These substituents may be substituted onthe alkyl group singly or in combination of two or more of them. Thesulfonic acid group and carboxylic acid group may form a salt with analkali metal ion or a quaternary ion of an organic amine. Thecombination of two or more substituents includes the case where theplural substituents are bonded to the alkyl group independently or thecase where the plural substituents are bonded to each other and thecombined substituents are bonded to the alkyl group.

As examples of the latter case, there are mentioned a sulfoalkoxyalkylgroup, a sulfoalkoxyalkoxyalkyl group, a carboxyalkoxyalkyl group and asulfophenylalkyl group.

As examples of R¹¹ and R¹², there are mentioned methyl, ethyl, n-propyl,n-butyl, vinylmethyl, 2-hydroxyethyl, 4-hydroxybutyl, 2-acetoxyethyl,3-acetoxypropyl, 2-methoxyethyl, 4-methoxybutyl, 2-carboxyethyl,3-carboxypropyl, 2-(2-carboxyethoxy)ethyl, 2-sulfoethyl, 3-sulfopropyl,3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl,2-(3-sulfopropoxy)ethyl, 2-acetoxy-3-sulfopropyl,3-methoxy-2-(3-sulfopropoxy)propyl, 2-[2-(3-sulfopropoxy)ethoxy]ethyland 2-hydroxy-3-(3'-sulfopropoxy)propyl groups.

As specific examples of the nitrogen-containing heterocyclic nuclei tobe formed by Z₁ or Z₂ in formula (VIa), there are mentioned oxazole,thiazole, selenazole, imidazole, pyridine, oxazoline, thiazoline,selenazoline and imidazoline nuclei, as well as condensed nuclei thereofwhich are condensed with a benzene ring, naphthalene ring or othersaturated or unsaturated carbon ring. The nitrogen-containinghetero-rings may have further substituent(s) (for example, an alkylgroup, a trifluoromethyl group, an alkoxycarbonyl group, a cyano group,a carboxylic acid group, a carbamoyl group, an alkoxy group, an arylgroup, an acyl group, a hydroxyl group, a halogen atom).

As the anion for X in formula (VIa), there are mentioned, for example,Cl⁻, Br⁻, I⁻, SO₄ ⁻⁻, NO₃ ⁻ and ClO₄ ⁻⁻.

Specific examples of the cyanine dyes of formula (VIa) which arepreferred for the yellow layer and cyan layer are mentioned below.##STR22##

Wherein "Et" represents an ethyl group.

Next, sensitizing dyes preferred for a greensensitive emulsion layer areshown below, which are represented by the following formula (VIb):##STR23## wherein Z₁ and Z₂ each represents an atomic group necessaryfor forming a benzene or naphthalene ring as condensed to thehetero-ring in the formula, and the condensed heterocyclic ring to beformed may be substituted by substituent(s);

R₁ and R₂ each represents an alkyl group, an alkenyl group or an arylgroup;

R₃ represents a hydrogen atom or an alkyl group having from 1 to 3carbon atoms;

X₁ ⁻ represents an anion;

p represents 0 or 1; and

Y₁ and Y₂ each represents an oxygen atom, a sulfur atom, a seleniumatom, a nitrogen atom or a tellurium atom.

Preferred substituents for the condensed heterocyclic nuclei of formula(VIb) include a halogen atom, an aryl group, an alkenyl group, an alkylgroup and an alkoxy group. Especially preferred substituents are ahalogen atom, a phenyl group and a methoxy group, and the most preferredsubstituent is a phenyl group.

Preferably, Z₁ and Z₂, of formula (VIb) both are benzene or thiazolerings as condensed to the oxazole ring. At least one benzene ring issubstituted by a phenyl group on its 5-position; or one benzene ring issubstituted by a phenyl group on its 5-position and the other benzenering is substituted by a halogen atom at its 5-position.

R₁ and R₂ in formula (VIb) each represents an alkyl group, an alkenylgroup or an aryl group. Preferably, they each represent an alkyl groupsubstituted by a carboxyl group or a sulfo group. More preferably, theyeach represent a sulfoalkyl group having from 1 to 4 carbon atoms. Mostpreferably, they are sulfoethyl groups. R₃ in formula (VIb) represents ahydrogen atom or an alkyl group having from 1 to 3 carbon atoms.Preferably, it is a hydrogen atom or an ethyl group.

The sensitizing dyes of formula (VIb) which can be used in the presentinvention can be combined with any other sensitizing dye to form aso-called supercolor sensitization system. In this case, the respectivedyes are dissolved in the same or different solvents and the resultingsolutions are blended prior to be added to the emulsion. Alternatively,the respective sensitizing dyes may be added to the emulsion separately.In the latter case of separately adding the dyes to the emulsion, theorder of the addition and the interval between the first addition of onedye to the next addition of another dye may freely be determined inaccordance with the object.

Specific examples of sensitizing dyes of the formula (VIb) are mentionedbelow, which, however, are not intended to restrict the scope of thesensitizing dyes employable in the present invention. ##STR24##

For spectral sensitization of silver halide emulsions, in general, amethod is employed where a spectral sensitizing dye is applied to silverhalide grains which have completely been formed so that the dye may beadsorbed on the surface of the grains. As opposed to this, U.S. Pat. No.2,735,766 illustrates a different method where a merocyanine dye isadded during formation of precipitates of silver halide grains and itmentions that the amount of dye which does not adsorb on to the grainsmay be reduced. JP-A-55-26589 illustrates a method of adding a spectralsensitizing dye to the reaction system during addition of an aqueoussilver salt solution and an aqueous halide solution whereby the dye isadsorbed on to the silver grains being formed. Accordingly, addition ofspectral sensitizing dyes may be effected during formation of silverhalide crystalline grains, or after formation thereof, or before theinitiation of formation of the grains. Precisely, addition of thespectral sensitizing dye before the initiation of formation of silverhalide grains refers to methods in which the spectral sensitizing dyesare added to the reactor prior to initiation of the reaction of formingsilver halide crystalline grains. Addition of the dye during formationof the grains refers to methods such as described in the above twopatent publications; and addition of the dye after formation of thegrains refers to methods in which the dye is added substantially aftercompletion of the grain-forming step and is adsorbed on to the alreadyformed grains.

The silver halide emulsion for use in the present invention can bechemically sensitized after formation of the grains, and addition of thespectral sensitizing dye also can be effected after completion of theformation of the grains. In general, the addition of the spectralsensitizing dye may be effected before initiation of the chemicalsensitization, or during the course of the chemical sensitization, orafter the chemical sensitization, or immediately before coating theemulsion on a support.

In accordance with the present invention, addition of the spectralsensitizing dye is preferably conducted during the course of at leastone step after the substantial completion of formation of the silverhalide grains so that the spectral sensitizing dye is adsorbed to thegrains. Addition of the spectral sensitizing dyes may be effected duringthe course of two or more steps or the dyes may be added separately intwo or more steps. Where the dye is added in one step, it may be addedintensively in a short period of time or it may be gradually andcontinuously added over a long period of time. Two or more of suchaddition methods may be combined in practical performance.

The spectral sensitizing dye may be added as it is in a crystalline orpowdery form, but it is preferably added in the form or a solution ordispersion prepared by an appropriate dissolving or dispersing method.Where the dye is formed into a solution, it may be dissolved in awater-soluble solvent such as an alcohol having from 1 to 3 carbonatoms, acetone, pyridine or methyl cellosolve or a mixed solventthereof. Surfactants may be employed for forming a micelle dispersioncontaining the dye. Other types of dispersions may also be prepared.

The amount of the spectral sensitizing dye to be added to the silverhalide emulsion for use in the present invention depends upon the objectof spectral sensitization and the content of the emulsion, in general,is from 1×10⁻⁶ mol to 1×10⁻² mol, more preferably from 1×10⁻⁵ mol to5×10⁻³ mol, per mol of the silver halide.

The emulsion for use in the present invention is generally physicallyripened, chemically ripened and spectrally sensitized. Additives to beused in these steps are described in Research Disclosure, Vol. 176, Item17643 (December, 1979) and ibid., Vol. 187, Item 18716 (November, 1979),and the relevant parts are shown in the Table set forth above.

In accordance with the present invention, various color couplers can beemployed, and examples thereof are described in patent publications asreferred to in Research Disclosure, Vol. 176, Item 17643, VII-C to G.

As yellow couplers for use in the present invention, for example, thosedescribed in U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024 and4,401,752 JP-A-58-10739 and British Patents 1,425,020 and 1,476,760 arepreferred.

As magenta couplers, 5-pyrazolone type and pyrazoloazole type compoundsare preferred and, for example, those described in U.S. Pat. Nos.4,310,619 and 4,351,897, European Patent 73,636, U.S. Pat. Nos.3,061,432 and 3,725,067, Research Disclosure, Item 24220 (June, 1984),JP-A-60-33552, Research Disclosure, Item 24230 (June, 1984),JP-A-60-43659 and U.S. Pat. Nos. 4,500,630 and 4,540,654 are especiallypreferred.

As cyan couplers, phenol type and naphthol type couplers are mentionedand, for example, those described in U.S. Pat. Nos. 4,052,212,4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West GermanPatent Application (OLS) No. 3,329,729, European Patent 121,365A, U.S.Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767 and EuropeanPatent 161,626A are preferred.

Colored couplers for correcting the unnecessary absorption of coloreddyes can also be employed in the present invention, and those describedin Research Disclosure, Vol. 176, Item 17643, VII-G, U.S. Pat. No.4,163,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258 andBritish Patent 1,146,368 are preferred.

Couplers giving a colored dye with pertinent diffusibility can also beemployed in the present invention, and those described in U.S. Pat. No.4,366,237, British Patent 2,125,570, European Patent 96,570 and WestGerman Patent Application (OLS) No. 3,234,533 are preferred.

Specific examples of polymerized dye-forming couplers which can beemployed in the present invention are described in U.S. Pat. Nos.3,451,820, 4,080,211 and 4,367,282 and British Patent 2,102,173.

Couplers which release a photographically useful residue during couplingcan also be preferably used in the present invention. For instance, DIRcouplers which release a development inhibitor which are described inpatent publications as referred to in Research Disclosure, Vol. 176,Item 17643, VII-F, JP-A-57-151944, JP-A 57-154234 and JP-A-60-184248 andU.S. Pat. No. 4,248,962 are preferred.

As couplers which imagewise release a nucleating agent or developmentaccelerator in development, those described in British Patents 2,097,140and 2,131,188 and JP-A-59-157638 and JP-A-59-170840 are preferred.

In addition, as other couplers which can be employed in the presentinvention, there are mentioned the competing couplers described in U.S.Pat. No. 4,130,427; the polyvalent couplers described in U.S. Pat. Nos.4,283,472, 4,338,393 and 4,310,618; the DIR redox compound-releasingcouplers described in JP-A-60-185950; and the couplers which release adye which recolor after being released, as described in European Patent173,302A.

The above-mentioned couplers can be introduced into the photographicmaterials of the present invention by various known dispersion methods.

For instance, an oil-in-water dispersion method may be employed for thepurpose, and examples of high boiling point solvents usable in such amethod are described in U.S. Pat. No. 2,322,027.

A latex dispersion method may also be employed, and the step and effectthereof as well as latexes to be used for impregnation in the method aredescribed in U.S. Pat. No. 4,199,363, and West German Patent Application(OLS) Nos. 2,541,274 and 2,541,230.

In accordance with the present invention, the following compounds arepreferably employed together with the above-mentioned couplers. Inparticular, such compounds are especially preferably employed incombination with pyrazoloazole couplers.

Specifically, compounds (F) which may chemically bond with the aromaticamine developing agent which remains after color development to give achemically inactive and substantially colorless compound and/orcompounds (G) which may chemically bond with the oxidation product ofthe aromatic amine developing agent which remains after colordevelopment to give a chemically inactive and substantially colorlesscompound are preferably employed simultaneously or singly. Employment ofsuch compounds is preferred, for example, for preventing stains whichare caused by formation of colored dyes by reaction between thedeveloping agent or the oxidation product thereof which remains in thefilm and the coupler which also remains therein during storage of theprocessed material and also for preventing other harmful side-reactions.

As the compounds (F), preferred are compounds which react withp-anisidine with a secondary reaction speed constant k2 (in trioctylphosphate at 80° C.) of from 1.0 liter/mol.sec to 1×10⁻⁵ liter/mol.sec.The secondary reaction speed constant can be measured by the methoddescribed in JP-A-63-158545.

If the value k2 is larger than the above range, the (F) compoundsthemselves would be unstable and would often react with gelatin andwater to decompose. On the other hand, if it is smaller than the aboverange, the reaction speed of the (F) compound with the remainingaromatic amine developing agent would be low and, as a result, theobject of the present invention to prevent the harmful side effects ofthe remaining aromatic amine developing agent could not be attained.

More preferred examples of such compounds (F) are those represented bythe following formula (FI) or (FII).

    R.sub.1 -(A).sub.n -X                                      (FI) ##STR25##

In these formulae (FI) and (FII), R₁ and R₂ each represents an aliphaticgroup, an aromatic group or a heterocyclic group; n represents 1 or 0; Arepresents a group capable of reacting with an aromatic amine developingagent to form a chemical bond; X represents a group capable of reactingwith an aromatic amine developing agent to be released; B represents ahydrogen atom, an aliphatic group, an aromatic group, a heterocyclicgroup, an acyl group or a sulfonyl group; and Y represents a group whichaccelerates addition of an aromatic amine developing agent to thecompound of formula (FII). R₁ and X; and Y and R₂ or B may be bonded toeach other to form a cyclic structure.

Typical methods of reacting the compound (F) and the remaining aromaticamine developing agent by chemical bond are a substitution reaction oran addition reaction.

Specific examples of the compounds of formulae (FI) and (FII) aredescribed in JP-A-63-158545, JP-A-62-283338, JP-A-64-2042 and JP-A-6486139 and are preferably employed in the present invention.

On the other hand, as a compound (G) which chemically bonds with theoxidation product of the aromatic amine developing agent which remainsafter color developement to give a chemically inert and substantiallycolorless compound, more preferred are those represented by thefollowing formula (GI):

    R-Z                                                        (GI)

wherein R represents an aliphatic group, an aromatic group or aheterocyclic group; and Z represents a nucleophilic group or a groupwhich releases a nucleophilic group after being decomposed in thephotographic material.

In the compounds of formula (GI), Z is preferably a group having anucleophilic nCH₃ I value (R. G. Pearson, et al, J. Am. Chem. Soc., 90,319 (1968)) of 5 or more or a group to be derived therefrom.

Specific examples of the compounds of the formula (GI) are described inEuropean Patent 255,722, JP-A-62-143048, JP-A-62-229145, JP-A-64-2042,JP-A-64-86139 and JP-A-64-57259 and Japanese Patent Application No.63-136724 are preferably used in the present invention.

The details of the combinations of the abovementioned compounds (G) andcompounds (F) are described in JP-A-64-86139.

Suitable supports which are employable in the present invention aredescribed in the above-mentioned Research Disclosure, Item 17643, page28, and ibid, Item 18716, from page 647, right column to page 648, leftcolumn.

The method of the present invention can be applied to color photographicmaterials, for example, color negative films, color reversal films(coupler-in-emulsion type, or couper in-developer type), color papers,color positive films, color reversal papers, color diffusion transferprocess films and direct positive color photographic materials. Inparticular, it is preferably applied to color negative films, colorreversal films and color reversal papers.

The present invention will be explained in more detail with reference tothe following examples, which, however, are not intended to restrict thescope of the present invention.

EXAMPLE 1

Plural layers mentioned below were coated on a paper support bothsurfaces of which were coated with polyethylene, to prepare amulti-layer color photographic paper sample. Coating compositions wereprepared as mentioned below.

Preparation of First Layer-Coating Composition

27.2 cc of ethyl acetate and 8.2 g of Solvent (Solv-3) were added to19.1 g of Yellow Coupler (ExY), 4.4 g of Color Image Stabilizer (Cpd-1)and 0.7 g of Color Image Stabilizer (Cpd-7) and dissolved, and theresulting solution was dispersed by emulsification in 185 cc of a 10 %aqueous gelatin solution containing 8 cc of 10 % sodiumdodecylbenzenesulfonate. On the other hand, the following twoblue-sensitive sensitizing dyes were added to a silver chlorobromideemulsion (cubic grains having a mean grain size of 0.85 μm and a grainsize distribution fluctuation coefficient of 0.07 and containing 1.0mol% of silver bromide locally on a part of the grain surface), each inan amount of 2.0×10⁻⁴ mol, and then the resulting emulsion wassulfur-sensitized. The previously prepared emulsified dispersion and thesulfur-sensitized emulsion were blended to prepare a first layer-coatingcomposition comprising the components mentioned below. The other coatingcompositions for the second layer to the seventh layer were alsoprepared in a similar manner. As the gelatin hardening agent for eachlayer, there was used 1-hydroxy-3,5-dichloro-s-triazine sodium salt.

The following spectral sensitizing dyes were used for the respectivelayers. ##STR26## (The above two were incorporated each in an amount of2.0 ×10⁻⁴ mol per mol of silver halide in the layer). ##STR27##(4.0×10⁻⁴ mol per mol of silver halide in the layer) and ##STR28##(7.0×10⁻⁵ mol per mol of silver halide in the layer) ##STR29## (0.9×10⁻⁴mol per mol of silver halide in the layer)

To the red-sensitive emulsion layer was added the following compound inan amount of 2.6×10⁻³ mol per mol of silver halide. ##STR30##

1-(5-Methylureidophenyl)-5-mercaptotetrazole was added to theblue-sensitive emulsion layer, green-sensitive emulsion layer andred-sensitive emulsion layer in an amount of 8.5×10⁻⁵ mol, 7.7×10⁻⁴ moland 2.5×10⁻⁴ mol, respectively.

The following dyes were added to the emulsion layers for the purpose ofanti-irradiation, each in an amount of 4 mg/m². ##STR31##

The respective layers comprised the compositions mentioned below. Theamount coated is represented by the unit of g/m². The amount of thesilver halide emulsion coated indicates the amount of silver therein.

    ______________________________________                                                                 Coated                                                                        Amount                                               ______________________________________                                        Support:                                                                      Polyethylene-laminated Paper                                                  (containing a white pigment (TiO.sub.2) and a blueish                         dye (ultramarine) in the polyethylene on the side                             of the first layer)                                                           First Layer: (Blue-sensitive Emulsion Layer)                                  Above-mentioned Silver Chlorobromide                                                                     0.30                                               Emulsion                                                                      Gelatin                    1.86                                               Yellow Coupler (ExY)       0.82                                               Color Image Stabilizer (Cpd-1)                                                                           0.19                                               Color Image Stabilizer (Cpd-7)                                                                           0.03                                               Solvent (Solv-3)           0.35                                               Second Layer: (Color Mixing Preventing Layer)                                 Gelatin                    0.99                                               Color Mixing Preventing Agent (Cpd-5)                                                                    0.08                                               Solvent (Solv-1)           0.16                                               Solvent (Solv-4)           0.08                                               Third Layer: (Green-sensitive Emulsion Layer)                                 Silver Chlorobromide Emulsion                                                                            0.25                                               (cubic grains having a grain size of 0.40 μm                               and a variation coefficient of 0.09                                           and containing 1 mol % of silver bromide                                      locally on a part of the grain surface)                                       Gelatin                    1.24                                               Magenta Coupler (ExM)      0.29                                               Color Image Stabilizer (Cpd-3)                                                                           0.09                                               Color Image Stabilizer (Cpd-4)                                                                           0.06                                               Solvent (Solv-2)           0.32                                               Solvent (Solv-7)           0.16                                               Fourth Layer: (Ultraviolet Absorbing Layer)                                   Gelatin                    1.58                                               Ultraviolet Absorbent (UV-1)                                                                             0.47                                               Color Mixing Preventing Agent (Cpd-5)                                                                    0.05                                               Solvent (Solv-5)           0.24                                               Fifth Layer: (Red-sensitive Emulsion Layer)                                   Silver Chlorobromide Emulsion (cubic grains                                                              0.21                                               having a grain size of 0.36 μm and                                         a variation coefficient of 0.11 and                                           containing 1.6 mol % of silver bromide                                        locally on a part of the grain surface)                                       Gelatin                    1.34                                               Cyan Coupler (ExC)         0.34                                               Color Image Stabilizer (Cpd-6)                                                                           0.17                                               Color Image Stabilizer (Cpd-7)                                                                           0.34                                               Color Image Stabilizer (Cpd-9)                                                                           0.04                                               Solvent (Solv-6)           0.37                                               Sixth Layer: (Ultraviolet Absorbing Layer)                                    Gelatin                    0.53                                               Ultraviolet Absorbent (UV-1)                                                                             0.16                                               Color Mixing Preventing Agent (Cpd-5)                                                                    0.02                                               Solvent (Solv-5)           0.08                                               Seventh Layer: (Protective Layer)                                             Gelatin                    1.33                                               Acryl modified Copolymer of Polyvinyl Alcohol                                                            0.17                                               (modification degree 17%)                                                     Liquid Paraffin            0.03                                               ______________________________________                                    

Compounds used above were as follows: ##STR32##

The sample thus prepared was called sample (1-A). Next, Samples (1-B) to(1-E) were prepared in the same manner, except that the anti-irradiationdyes (I-4) and (I-36) were replaced by the following dyes.

    ______________________________________                                                                      Amount                                          Sample                        Added                                           Code    Anti-irradiation Dye Used                                                                           (mg/m.sup.2)                                    ______________________________________                                        (I-A)   (I-4)                 4                                                        (I-36)               4                                               (I-B)   (I-1)                 4                                                       (I-7)                 4                                               (I-C)   (I-4)                 4                                                       (I-8)                 4                                               (I-D)                                                                                  ##STR33##            8                                               (I-E)                                                                                  ##STR34##            8                                               ______________________________________                                    

In order to examine the photographic characteristics of the thusprepared Samples (1-A) to (1-E), the following experiment was carriedout.

First, the samples were sensitometrically wedgewise exposed by the useof a photo sensitometer (FWH Type, manufactured by Fuji Photo Film Co.Ltd.; color temperature of the light source 3200° K.), whereuponexposure was effected for an exposing time of 1/10 second with anexposing amount of 250 CMS.

The thus exposed samples were then processed by the use of an automaticdeveloping machine in accordance with the steps mentioned below, usingthe processing solutions also mentioned below. The composition of thecolor developer was varied as indicated in Table 1 below.

    ______________________________________                                        Processing Steps Temperature                                                                              Time                                              ______________________________________                                        Color Development                                                                              38° C.                                                                            45 sec                                            Bleach-fixation  30 to 36° C.                                                                      30 sec                                            Rinsing (1)      30 to 37° C.                                                                      20 sec                                            Rinsing (2)      30 to 37° C.                                                                      20 sec                                            Rinsing (3)      30 to 37° C.                                                                      20 sec                                            Drying           70 to 80° C.                                                                      60 sec                                            ______________________________________                                    

The rinsing was effected by a three-tank countercurrent system from therinsing tank (3) to the rinsing tank (1).

The processing solutions used in the above steps were as follows:

    ______________________________________                                        Color Developer:                                                              Water                      800     ml                                         Ethylenediamine-N,N,N,N-tetramethylene-                                                                  3.0     g                                          phosphonic Acid                                                               Preservative (III-19)      5.0     g                                          Sodium Chloride            See Table 1                                        Potassium Bromide          See Table 1                                        Potassium Carbonate        25      g                                          N-ethyl-N-(β-methanesulfonamidoethyl)-                                                              5.0     g                                          3-methyl-4-aminoaniline Sulfate                                               Triethanolamine            10.0    g                                          Brightening Agent (WHITEX 4, manufactured                                                                2.0     g                                          by Sumitomo Chemical Co.)                                                     Water to make              1000    ml                                         pH (25° C.)         10.05                                              Bleach-fixing Solution:                                                       Water                      400     ml                                         Ammonium Thiosulfate (70 wt. %)                                                                          100     ml                                         Sodium Sulfite             17      g                                          Ammonium Ethylenediaminetetraacetato/iron(III)                                                           55      g                                          Disodium Ethylenediaminetetraacetate                                                                     5       g                                          Glacial Acetic Acid        9       g                                          Water to make              1000    ml                                         pH (25° C.)         5.40                                               ______________________________________                                    

Rinsing Solution Ion-exchanged Water (Calcium content and magnesiumcontent each was 3 ppm or less.)

After being processed as mentioned above, the minimum density andmaximum density of cyan (R) (D_(R) min, D_(R) max) were measured With aMacbeth densitometer in each sample. In addition, the amount of theresidual silver in the maximum density was measured with an fluorescentX-ray in each sample. The results are shown in Table 1 below.

                                      TABLE 1                                     __________________________________________________________________________    Process No.   1   2    3     4     5    6     7     8    9                    __________________________________________________________________________    Developer                                                                           NaCl (mol/l)                                                                          --  3 × 10.sup.-2                                                                3.5 × 10.sup.-2                                                                 6 × 10.sup.-2                                                               1 × 10.sup.-1                                                                1.5 × 10.sup.-1                                                                 2 × 10.sup.-1                                                               6 × 10.sup.-2                                                                --                         KBr (mol/l)                                                                           --  2 × 10.sup.-5                                                                3.5 × 10.sup.-5                                                               2.5 × 10.sup.-4                                                               5 × 10.sup.-4                                                                1.0 × 10.sup.-3                                                               1.5 × 10.sup.-3                                                               --   2.5 ×                                                                   10.sup.-4            Sample                                                                              D.sub.R min                                                                           0.16                                                                              0.14 0.11  0.,10 0.10 0.10  0.10  0.13 0.13                 (I-A) D.sub.R max                                                                           2.35                                                                              2.35 2.35  2.35  2.35 2.33  2.01  2.15 2.15                       Residual Silver                                                                       7.9 5.8  2.1   1.8   1.8  1.8   3.5   6.0  7.1                        (μg/cm.sup.2)                                                        (I-B) D.sub.R min                                                                           0.16                                                                              0.13 0.11  0.10  0.10 0.10  0.10  0.13 0.13                       D.sub.R max                                                                           2.35                                                                              2.35 2.35  2.35  2.35 2.32  1.98  2.14 2.15                       Residual Silver                                                                       8.0 6.1  2.2   1.9   1.8  1.8   4.5   6.3  6.0                        (μg/cm.sup.2)                                                        (I-C) D.sub.R min                                                                           0.16                                                                              0.14 0.11  0.10  0.10 0.10  0.10  0.14 0.14                       D.sub.R max                                                                           2.34                                                                              2.34 2.34  2.34  2.34 2.33  2.05  2.13 2.15                       Residual Silver                                                                       7.6 5.7  1.9   1.6   1.6  1.6   5.9   5.8  5.9                        (μg/cm.sup.2)                                                        (I-D) D.sub.R min                                                                           0.16                                                                              0.15 0.14  0.14  0.14 0.14  0.14  0.15 0.15                       D.sub.R max                                                                           2.29                                                                              2.30 2.30  2.30  2.15 2.10  2.05  2.15 2.13                       Residual Silver                                                                       5.9 6.0  6.0   6.0   6.0  5.9   5.8   5.9  5.9                        (μg/cm.sup.2)                                                        (I-E) D.sub.R min                                                                           0.17                                                                              0.16 0.15  0.15  0.15 0.15  0.15  0.15 0.16                       D.sub.R max                                                                           2.30                                                                              2.31 2.31  2.30  2.17 2.09  2.00  2.16 2.17                       Residual Silver                                                                       6.3 6.2  6.1   6.1   6.0  6.0   6.0   6.2  6.2                        (μg/cm.sup.2)                                                        __________________________________________________________________________

Where Samples (1 A), (1-B) and (1-C) of the present invention wereprocessed in accordance with processes (3), (4), (5) or (6) of themethod of the present invention, the stains in the cyan color weresmall, the maximum density was high, the amount of the residual silverwas small, and excellent photographic characteristics were obtained.

Where Samples (1-D) and (1-E) each having an antiirradiation dye fallingoutside the scope of the present invention were processed by the methodof the present invention, the above-mentioned effect could not beobtained.

EXAMPLE 2

Sample (1-A) was processed by process (4) of Example 1, except thatPreservative (III-19) was replaced by the same molar amount of otherpreservatives, namely, (II-1), (II-2), (III-11) or (III-21),respectively, and when so processed the same excellent photographiccharacteristics were obtained.

EXAMPLE 3

Samples were prepared in the same manner as Sample (1 A), except thatanti-irradiation dyes (I-1), (I-3), (I-5), (I-9), (I-12), (I-18),(I-25), (I-30) or (I-37) was incorporated each in an amount of 8 mg/m²in place of the anti-irradiation dyes in Sample (1-A), and these wereprocessed by one of the processes (3) to (6). As a result, excellentphotographic characteristics were obtained.

EXAMPLE 4

Samples (4-A), (4-B), (4-C) and (4-D) were prepared in the same manneras Sample (1-A) in Example 1, except that the silver bromide content wasvaried as indicated in the following Table. These were then processed inaccordance with processes (2), (4) and (7) of Example 1. The resultsobtained are shown in Table 2 below.

    ______________________________________                                                 Blue-sensitive                                                                            Green-sensitive                                                                           Red-sensitive                                         Layer       Layer       Layer                                        Sample Code                                                                            (Br mol %)  (Br mol %)  (Br mol %)                                   ______________________________________                                        (1-A)     1.0         1.0         1.6                                         (4-A)     5.0         5.0         5.0                                         (4-B)    10.0        10.0        10.0                                         (4-C)    20.0        20.0        20.0                                         (4-D)    30.0        30.0        30.0                                         ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Process No.     2        4         7                                          ______________________________________                                        Developer                                                                             NaCl (mol/l)                                                                              3 × 10.sup.-2                                                                      6 × 10.sup.-2                                                                   2 × 10.sup.-1                            KBr(mol/)   2 × 10.sup.-5                                                                    2.5 × 10.sup.-4                                                                 1.5 × 10.sup.-3                    Sample  D.sub.R min 0.14     0.10    0.10                                     (I-A)   D.sub.R max 2.35     2.35    2.01                                             Residual Silver                                                                           5.8      1.8     3.5                                              (μg/cm.sup.2)                                                              D.sub.R min 0.15     0.10    0.10                                     (4-A)   D.sub.R max 2.29     2.30    2.00                                             Residual Silver                                                                           5.3      1.8     4.0                                              (μg/cm.sup.2)                                                              D.sub.R min 0.15     0.11    0.11                                     (4-B)   D.sub.R max 2.25     2.30    1.90                                             Residual Silver                                                                           5.1      2.0     4.1                                              (μg/cm.sup.2)                                                              D.sub.R min 0.15     0.12    0.12                                     (4-C)   D.sub.R max 2.24     2.29    1.81                                             Residual Silver                                                                           5.0      2.3     4.2                                              (μg/cm.sup.2)                                                              D.sub.R min 0.16     0.15    0.15                                     (4-D)   D.sub.R max 2.18     1.95    1.76                                             Residual Silver                                                                           5.0      4.9     4.8                                              (μ g/cm.sup.2)                                                     ______________________________________                                    

Where Samples (1-A), (4-A), (4-B) and (4-C) of the present inventionwere processed by process (4) of the method of the present invention,the stains were small, the maximum density was high and the amount ofthe residual silver was small, and excellent photographiccharacteristics were obtained. In particular, the effect was noticeablein Samples (1-A) and (4-A) each having a silver chlorobromide emulsionhaving a chloride ion content of 95 mol% or more.

EXAMPLE 5

Plural layers mentioned below were coated on a paper support bothsurfaces of which were coated with polyethylene, to prepare amulti-layer color photographic paper sample. Coating compositions wereprepared as mentioned below.

Preparation of First Layer-Coating Composition

27.2 cc of ethyl acetate and 8.2 g of Solvent (Solv-3) were added to19.1 g of Yellow Coupler (ExY), 4.4 g of Color Image Stabilizer (Cpd-1)and 0.7 g of Color Image Stabilizer (Cpd-7) and dissolved, and theresulting solution was dispersed by emulsification in 185 cc of a 10 %aqueous gelation solution containing 8 cc of 10 % sodiumdodecylbenzenesulfonate. On the other hand, the following two bluesensitive sensitizing dyes were added to a silver chlorobromide emulsion(cubic grains having a mean grain size of 0.88 μm and a grain sizedistribution variation coefficient of 0.08 and containing 0.2 mol% ofsilver bromide on the grain surface), each in an amount of 2.0×10⁻⁴ mol,and then the resulting emulsion was sulfur-sensitized. The previouslyprepared emulsified dispersion and the sulfur-sensitized emulsion wereblended to prepare a first layer-coating composition comprising thecomponents mentioned below. The other coating compositions for thesecond layer to the seventh layer were also prepared in a similarmanner. As the gelatin hardening agent for each layer, there was used1-hydroxy-3,5-dichloro-s-triazine sodium salt.

The following spectral sensitizing dyes were used for the respectivelayers. ##STR35## (The above two were incorporated each in an amount of2.0 ×10⁻⁴ mol per mol of silver halide in the layer.) ##STR36##

To the red-sensitive emulsion layer was added the following compound inan amount of 2.6×10⁻³ mol per mol of silver halide. ##STR37##

1-(5-Methylureidophenyl)-5-mercaptotetrazole was added to theblue-sensitive emulsion layer, green-sensitive emulsion layer andred-sensitive emulsion layer in an amount of 8.5×10⁻⁵ mol, 7.7×10⁻⁴ moland 2.5×10⁻⁴ mol, per mol of silver halide, respectively.

The following dyes were added to the emulsion layers for the purpose ofanti-irradiation, each in an amount of 4 mg/m². ##STR38##

The respective layers comprised the compositions mentioned below. Theamount coated is represented by the unit of g/m². The amount of thesilver halide emulsion coated indicates the amount of silver therein.

    __________________________________________________________________________    Support:                                                                      Polyethylene-laminated Paper (containing a white pigment (TiO.sub.2) and      a blueish dye (ultramarine) in the polyethylene on the side of the first      layer)                                                                                                        Coated Amount                                 __________________________________________________________________________    First Layer: (Blue-sensitive Emulsion Layer)                                  Silver Chlorobromide Emulsion   0.30                                          Gelatin                         1.86                                          Yellow Coupler (ExY')           0.82                                          Color Image Stabilizer (Cpd-1') 0.19                                          Solvent (Solv-3')               0.35                                          Color Image Stabilizer (Cpd-7') 0.06                                          Second Layer: (Color Mixing Preventing Layer)                                 Gelatin                         0.99                                          Color Mixing Preventing Agent (Cpd-5')                                                                        0.08                                          Solvent (Solv-1')               0.16                                          Solvent (Solv-4')               0.03                                          Third Layer: (Green-sensitive Emulsion Layer)                                 Silver Chlorobromide Emulsion   0.12                                          (1/3 mixture (by mol of Ag) of cubic grains having a mean grain size          of 0.55 μm and a grain size distribution variation coefficient of 0.10     and cubic grains having a mean grain size of 0.39 μm and a grain           size distribution variation coefficient of 0.08; both grains containing       0.8 mol % of AgBr locally on the grain surface)                               Gelatin                         1.24                                          Magenta Coupler (ExM')          0.27                                          Color Image Stabilizer (Cpd-3') 0.15                                          Color Image Stabilizer (Cpd-8') 0.02                                          Color Image Stabilizer (Cpd-9') 0.03                                          Solvent (Solv-2')               0.54                                          Fourth Layer: (Ultraviolet Absorbing Layer)                                   Gelatin                         1.58                                          Ultraviolet Absorbent (UV-1')   0.47                                          Color Mixing Preventing Agent (Cpd-5')                                                                        0.47                                          Solvent (Solv-5')               0.24                                          Fifth Layer: (Red-sensitive Emulsion Layer)                                   Silver Chlorobromide Emulsion   0.23                                          (1/4 mixture (by mol of Ag) of cubic grains having a mean grain size          of 0.58 μm and grain size distribution variation coefficient of 0.09       and cubic grains having a mean grain size of 0.45 μm and a grain           size distribution variation coefficient of 0.11; both grains containing       0.6 mol % of AgBr locally on a part of the grain surface)                     Gelatin                         1.34                                          Cyan Coupler (ExC')             0.32                                          Color Image Stabilizer (Cpd-6') 0.17                                          Color Image Stabilizer (Cpd-10')                                                                              0.04                                          Color Image Stabilizer (Cpd-7') 0.40                                          Solvent (Solv-6')               0.15                                          Sixth Layer: (Ultraviolet Absorbing Layer)                                    Gelatin                         0.53                                          Ultraviolet Absorbent (UV-1')   0.16                                          Color Mixing Preventing Agent (Cpd-5')                                                                        0.02                                          Solvent (Solv-5')               0.08                                          Seventh Layer: (Protective Layer)                                             Gelatin                         1.33                                          Acryl-modified Copolymer of Polyvinyl Alcohol                                                                 0.17                                          (modification degree 17%)                                                     Liquid Paraffin                 0.03                                          __________________________________________________________________________    Compounds used above were as follows:                                         Yellow Coupler (ExY'):                                                         ##STR39##                                                                    Magenta Coupler (ExM'):                                                        ##STR40##                                                                    Cyan Coupler (ExC'):                                                          2/4/4 mixture (by weight) of the following compounds:                          ##STR41##                                                                     ##STR42##                                                                    Color Image Stabilizer (Cpd-1'):                                               ##STR43##                                                                    Color Image Stabilizer (Cpd-3'):                                               ##STR44##                                                                    Color Mixing Preventing Agent (Cpd-5'):                                        ##STR45##                                                                    Color Image Stabilizer (Cpd-6'):                                              2/4/4 mixture (by weight) of the following compounds:                          ##STR46##                                                                     ##STR47##                                                                     ##STR48##                                                                    Color Image Stabilizer (Cpd-7'):                                               ##STR49##                                                                    Color Image Stabilizer (Cpd-8'):                                               ##STR50##                                                                    Color Image Stabilizer (Cpd-9'):                                               ##STR51##                                                                    Color Image Stabilizer (Cpd-10'):                                              ##STR52##                                                                    Ultraviolet Absorbent (UV-1'):                                                4/2/4 mixture (by weight) of the following compounds:                          ##STR53##                                                                     ##STR54##                                                                     ##STR55##                                                                    Solvent (Solv-1'):                                                             ##STR56##                                                                    Solvent (Solv-2'):                                                            2/1 mixture (by volume) of the following compounds:                            ##STR57##                                                                    Solvent (Solv-3'):                                                            OP(OC.sub.9 H.sub.19 (iso)).sub.3                                             Solvent (Solv-4'):                                                             ##STR58##                                                                    Solvent (Solv-5'):                                                             ##STR59##                                                                    (Solv-6'):                                                                     ##STR60##                                                                           The sample thus prepared was called Sample ( 5A). Nest, Sample         (5B) was prepared in the same manner, except that the same                

Samples (5-A) and (5-B) were imagewise exposed and then continuouslyprocessed in accordance with the processing steps mentioned below untilthe amount of the replenisher added to the color developer tank reachedthree times of the capacity of the developer tank.

    ______________________________________                                                                     Amount of                                        Processing                   Replenisher                                                                            Tank                                    Step      Temp.      Time    (*)      Capacity                                ______________________________________                                        Color     38 C.      45 sec  109 ml   4 liters                                Development                                                                   Bleach-fixation                                                                         30 to 36° c.                                                                      45 sec   61 ml   4 liters                                Rinsing (1)                                                                             30 to 37° C.                                                                      30 sec  --       2 liters                                Rinsing (2)                                                                             30 to 37° C.                                                                      30 sec  --       2 liters                                Rinsing (3)                                                                             30 to 37° C.                                                                      30 sec  364 ml   2 liters                                Drying    70 to 85° C.                                                                      60 sec                                                   ______________________________________                                         (*) Per m.sup.2 of Sample Processed.                                     

The rinsing was effected by a three-tank countercurrent system from therinsing tank (3) to the rinsing tank (1). The rinsing solution in therinsing tank (1) was replenished to the bleach-fixing bath in an amountof 122 ml/m² of the sample being processed.

The processing solutions used in the above steps were as follows:

    ______________________________________                                                               Tank     Re-                                           Color Developer:       Solution plenisher                                     ______________________________________                                        Water                  800    ml    800  ml                                   Ethylenediamine-N,N,N',N'-tetramethylene-                                                            3.0    g     3.0  g                                    phosphonic Acid                                                               Triethanolamine        8.0    g     11.0 g                                    Sodium Chloride        4.2 ×                                                                            --                                                                   10.sup.-2 M                                            Potassium Bromide      1.3 ×                                                                   10.sup.-4 M                                                                            --                                            Potassium Carbonate    25     g     25   g                                    N-ethyl-N-(-methanesulfon-                                                                           5.0    g     9.5  g                                    amidoethyl)-3-methyl-4-amino-                                                 aniline Sulfate                                                               Organic Preservative (III-19)                                                                        2.7 ×                                                                            5.4 ×                                                          10.sup.-2 M                                                                            10.sup.-2 M                                   Brightening Agent (WHITEX-4,                                                                         1.25   g     2.5  g                                    manufactured by Sumitomo                                                      Chemical Co.)                                                                 Water to make          1000   ml    1000 ml                                   pH (25° C.)     10.05        10.60                                     ______________________________________                                    

    ______________________________________                                                              Tank                                                    Bleach-fixing Solution:                                                                             Solution Replenisher                                    ______________________________________                                        Water                 400    ml                                               Ammonium Thiosulfate (70 wt. %)                                                                     100    ml    250   ml                                   Ammonium Sulfite      38     g     95    g                                    Ammonium              55     g     138   g                                    Ethylenediaminetetraacetate/Iron(III)                                         Ammonium Bromide      30     g     75    g                                    Disodium ethylenediaminetetraacetate                                                                5      g     10    g                                    Glacial Acetic Acid   9      g     20    g                                    Water to make         1000   ml    1000  ml                                   pH (25° C.)    5.40         5.40                                       ______________________________________                                    

Rinsing Solution: Tank solution and replenisher were same.

Ion-exchanged Water (Calcium content and magnesium content each was 3ppm or less.)

In continuous processing, distilled water was added to the colordevelopment tank, bleach-fixing tank and rinsing tank each in an amountequal to the amount which was evaporated out from the respective tanksfor compensation of the evaporated and concentrated amount.

After the continuous processing, the chloride ion concentration and thebromide ion concentration in the respective color developers wereanalyzed and, as a result, they were equally as follows:

    ______________________________________                                                       Cl.sup.-  Br.sup.-                                             ______________________________________                                        After Continuous Processing of                                                                 5.5 × 10.sup.-2 M                                                                   2.0 × 10.sup.-4 M                          Sample (5-A)                                                                  After Continuous Processing of                                                                 5.5 × 10.sup.-2 M                                                                   2.0 × 10.sup.-4 M                          Sample (5-B)                                                                  ______________________________________                                    

Next, Samples (5-A) and (5-B) were sensitometrically exposed in the samemanner as in Example 1 and then processed with the respective processingsolution. The Values of D_(R) min and D_(R) max and the residual silveramount were measured, which were as follows:

    ______________________________________                                                                        Residual Ag                                   Sample No.    D.sub.R min                                                                             D.sub.R max                                                                           (μg/cm.sup.2)                              ______________________________________                                        5-A (the Invention)                                                                         0.11      2.34    0.8                                           5-B (Comparative)                                                                           0.18      2.28    4.9                                           ______________________________________                                    

As is obvious from the above-mentioned results, the photographiccharacteristics of the sample of the present invention (5-A) asprocessed by the method of the present invention were superior to thoseof the comparative sample (5-B) as the stains were small, the maximumdensity is high and the residual silver amount was small.

EXAMPLE 6

Samples (6-A), (6-B), (6-C), (6-D), (6-E) and (6-F) were prepared in thesame manner as Sample (5-A) of Example 5, except that theanti-irradiation dyes and the sensitizing dyes were varied as indicatedin Table 3 below.

                                      TABLE 3                                     __________________________________________________________________________                                          Sensitizing-Dyes                                                              Blue-                                                                              Green-                                                                             Red-                                                                sensitive                                                                          sensitive                                                                          sensitive                     Sample                                                                             Anti-irradiation Dyes   (Amount Added)                                                                         Layer                                                                              Layer                                                                              Layer                         __________________________________________________________________________    (6-A)                                                                               ##STR61##              (8 mg/m.sup.2)                                                                         VIa-41                                                                             VIb-35 VIb-36                                                                      VIa-42                        (6-B)                                                                               ##STR62##              (8 mg/m.sup.2)                                                                         VIa-41                                                                             VIb-35 VIb-36                                                                      VIa-42                        (6-C)                                                                              (I-2)                   (4 mg/m.sup.2)                                                                         S-A  S-B  S-C                                (I-4)                   (4 mg/m.sup.2)                                   (6-D)                                                                               (I-36)                 (4 mg/m.sup.2)                                                                         S-A  S-B  S-C                                 (I-37)                 (4 mg/m.sup.2)                                   (6-E)                                                                              (I-2)                   (4 mg/m.sup.2)                                                                         VIa-41                                                                             VIb-35                                                                             VIa-42                             (I-4)                   (4 mg/m.sup.2)                                                                              VIb-36                             (6-F)                                                                               (I-36)                 (4 mg/m.sup.2)                                                                         VIa-41                                                                             VIb-35                                                                             VIa-42                              (I-37)                 (4 mg/m.sup.2)                                                                              VIb-36                             __________________________________________________________________________     S-A                                                                           ##STR63##                                                                     SB                                                                            ##STR64##                                                                     SC                                                                            ##STR65##                                                                

These samples were sensitometrically exposed and then processed with thesame processing solution as those used for processing Sample (5-A) inExample 5. The values of D_(B) min, D_(R) max and D_(B) max (D_(B) isthe density of yellow) and the residual silver amount were measured,which were shown in Table 4 below.

                  TABLE 4                                                         ______________________________________                                                                              Residual                                Sample                                Ag amount                               Code   Remarks    D.sub.B min                                                                           D.sub.R min                                                                         D.sub.B max                                                                         (μg/cm.sup.2)                        ______________________________________                                        (6-A)  Comparison 0.15    0.17  1.95  4.8                                     (6-B)  "          0.15    0.16  1.97  4.9                                     (6-C)  Invention  0.12    0.12  2.08  2.5                                     (6-C)  "          0.12    0.12  2.10  2.4                                     (6-E)  "          0.10    0.11  2.15  0.9                                     (6-F)  "          0.10    0.11  2.15  1.0                                     ______________________________________                                    

As is obvious from the above-mentioned results, not only an excellentwhite background with less yellow stains and cyan stains was obtained,but also the maximum density was high and the residual silver amount wassmall in the samples of the present invention as processed by the methodof the present invention. The effect was especially remarkable inSamples (6-E) and (6-F), each having particularly favorable sensitizingdyes.

While the invention had been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changed and modifications can be made therein withoutdeparting from the spirit and scope thereof. PG,162

What is claimed is:
 1. A method for processing an imagewise exposedsilver halide color photographic material comprising at least one silverhalide emulsion layer, which comprises developing said silver halidecolor photographic material with a color developer containing at leastone aromatic primary amine color developing agent, wherein saidphotographic material contains (a) at least one high silver chloridecontent emulsion layer with a silver chloride content of 80 mol% ormore, and (b) a compound of formula (I): ##STR66## wherein R¹ and R₂each represents --COOR₅, ##STR67## --COR₅, --CN or a halogenatedmethane; R₃ and R₄ each represents a hydrogen atom or an unsubstitutedor substituted alkyl group; R₅ and R₆ each represents a hydrogen atom,an unsubstituted or substituted alkyl group having 1 to 10 carbon atomsor an unsubstituted or substituted aryl group having 6 to 10 carbonatoms; Q₁ and Q₂ each represents an unsubstituted or substituted arylgroup having 6 to 10 carbon atoms; X₁ and X₂ each represents a chemicalbond or a divalent linking group; Y₁ and Y₂ each represents a sulfogroup or a carboxy group; L₁, L₂ and L₃ each represents a methine group;m₁ and m₂ each represents 0, 1 or 2; n represents 0, 1 or 2; p₁ and p₂each represents 0, 1, 2, 3 or 4; s₁ and s₂ each represents 1 or 2; andt₁ and t₂ each represents 0 or 1; provided that the total of m₁, p₁ andt₁ and the total of m₂, p₂ and t₂ must not be 0 at the same time;andsaid color developer contains a chloride ion in an amount of from3.5×10⁻² to 1.5×10⁻¹ mol/liter and a bromide ion in an amount of from3.0×10⁻⁵ to 1.0×10⁻³ mol/liter: wherein the color developer contains anorganic preservative which retards the deteriorating speed of thearomatic primary amine color developing agent contained in thedeveloper; and wherein the organic preservative is a compound of formula(II) ##STR68## wherein R²¹ and R²² each represents a hydrogen atom, anunsubstituted or substituted alkyl group, an unsubstituted orsubstituted alkenyl group, an unsubstituted or substituted aryl group oran unsubstituted or substituted hetero-aromatic group, R²¹ and R²² mustnot be hydrogens at the same time, and they may be bonded to each otherto form a hetero-ring together with the adjacent nitrogen atom; thecyclic structure of the hetero-ring is 5-membered or 6-membered, and itis composed of carbon, hydrogen, halogen, oxygen, nitrogen and/or sulfuratoms, and may be either saturated or unsaturated.
 2. The methodaccording to claim 1, wherein the compound of formula (I) is present inthe color photographic material in an amount of from 0.0001 g to 1 g perm² of the material.
 3. The method according to claim 1, wherein theorganic preservative is at least one compound selected from ahydroxylamine derivative excluding unsubstituted hydroxylamine, ahydroxamic acid, a hydrazine, a hydrazide, a phenol, an α-hydroxyketone,an α-aminoketone, a saccaride, a monoamine, a diamine, a polyamine, aquaternary ammonium salt, a nitroxy radical, an alcohol, an oxime, adiamide compound, and a condensed ring amine.
 4. The method according toclaim 1, wherein the organic preservative is present in the colordeveloper in an amount of from 0.005 mol/liter to 0.5 mol/liter.
 5. Themethod according to claim 1, wherein the color developer furthercontains an organic preservative which is a compound of formula (IV):##STR69## wherein R⁷¹, R⁷² and R⁷³ each represents a hydrogen atom, analkyl group, an alkenyl group, an aryl group, an aralkyl group or aheterocyclic group; and R⁷¹ and R⁷² ; R⁷¹ and R⁷³ ; or R⁷² and R⁷³ maybe bonded to each other to form a nitrogen-containing hetero-ring; andR⁷¹, R⁷² and R⁷³ may have a substituent.
 6. The method according toclaim 1, wherein the color photographic material contains at least onesensitizing dye selected from formulae (VIa) or (VIb): ##STR70## whereinL represents an unsubstituted methine group or a substituted methinegroup;R¹¹ and R¹² each represents an unsubstituted alkyl group or asubstituted alkyl group; Z¹ and Z² each represents an atomic groupnecessary for forming a nitrogen-containing 5-membered or 6-memberedheterocyclic nucleus; X represents an anion; n represents a numericalvalue of 1, 3 or 5; n₁ and n₂ each represents 0 or 1; when n is 5, bothn₁ and n₂ are 0 and when n is 3, either n₁ or n₂ is 0; m represents 0 or1, but m is 0 when the compound forms an inner salt; when n is 5, theplural L groups may be bonded to each other to form a substituted orunsubstituted 5-membered or 6-membered ring; ##STR71## wherein Z₁ and Z₂in formula (VIb) each represents an atomic group necessary for forming abenzene or naphthalene ring as condensed to the hetero-ring in theformula, and the condensed heterocyclic ring to be formed may besubstituted by a substituent; R₁ and R₂ in formula (VIb) each representsan alkyl group, an alkenyl group or an aryl group; R₃ in formula (VIb)represents a hydrogen atom or an alkyl group having from 1 to 3 carbonatoms; X₁ - in formula (VIb) represents an anion; p in formula (VIb)represents 0 or 1; and Y₁ and Y₂ in formula (VIb) each represents anoxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or atellurium atom.